FR2602786A1 - PROCESS FOR PREPARING EXTREME-PRESSURE ADDITIVES - Google Patents

Abstract

THE PRESENT INVENTION RELATES TO A PROCESS FOR PREPARING EXTREME PRESSURE ADDITIVES. THE ADDITIVE MEETS THE GENERAL FORMULA: (RI-VAR) (S) IN WHICH: R, R ... R REPRESENT HYDROGEN, GROUPS OF HYDROCARBONS CONTAINING 1 TO 40 ATOMS OF CARBON; AR REPRESENTS GROUPS OF AROMATIC HYDROCARBONS WITH 1 OR MORE CORES; B 1 A 5, C 2 A 10, D 1 A 9, AND X 1 A 6 AND IS PREPARED BY REACTING ORGANIC CHLORIN COMPOUNDS OF FORMULA (RI-V-AR) -CL, ON METAL SULPHIDES OF FORMULA MS AND BY CHLOROMETHYLANT OF HYDROCARBONS OF FORMULA RI-V-AR WITH A SOLUTION OF FORMALDEHYDE AND HYDROCHLORIC ACID. APPLICATION: PREPARATION OF LUBRICATING AND HYDRAULIC OILS.

Description

The present invention relates to a process for preparing an EP additive

  (extreme pressure) suitable for preparing lubricating and hydraulic oils, pasty lubricants (greases), and lubricating and cooling liquids of high sulfur content from chloromethylated alkylaromatic compounds. Lubricants intended for vehicles, engines, industrial plants, hydraulic systems and metalworking are produced in a widespread manner with 0.1 to 20% EP additive to protect tools and apparatus. , to reduce wear and to achieve economically profitable operation. These compounds, which usually contain sulfur, chlorine, phosphorus, and nitrogen, react chemically with metals, producing a protective layer on the surface that prevents the formation of local microswings between the metal surfaces that produce a relative movement in mutual contact. Such microswings occur because of the high temperature thermal peaks that are due to the high load; when they break, the surface undergoes pitting or sanding. Apart from the wear protection effect, other important properties must also be taken into account, for example the lubricating power, the thermal stability, the protection effect against oxidation and corrosion. These properties are obtained in part by means of compound effect compounds,

  partly by means of additive compositions.

  In the specialized literature on lubricants, in particular in the Patents, numerous methods for the preparation of EP additives which can be classified have been described.

in three distinct groups.

  1) Alkanols, esters, alkylphenol derivatives, olefins and / or hydrocarbons containing sulfur, or chlorine or nitrogen as hetero atoms, are reacted with phosphorus and sulfur compounds by for example on P4S10 (see, for example, RDA Patents No. 117,248, Nos. 101,695 and 79,093, US Patent No. 4,058,468 and Hungarian Patent No. 180,272). An additive containing in the first place sulfur and phosphorus thus prepared is certainly only weakly active as an additive EP, but it has advantageous additional properties, for example a

  protective effect against oxidation and corrosion.

  2) Alkenes are reacted with one or more unsaturated bonds (unsaturations), aromatic and / or alkylaromatic hydrocarbons, hydrocarbons containing, as hetero atoms, sulfur, chlorine, nitrogen, phosphorus, esters on chlorinated sulfur compounds (SC12, S2C12, SOC12 or RS-C1). In some cases, the reaction product is further treated to remove the residual chlorine content with sodium hydroxide, sodium mercaptide or sodium sulfide. Such methods are described in U.S. Patent Nos. 4,198,305, 4,097,387, 3,925,414, 3,844,964 and 3,873,454, and in French Patent No. 2,404,042. The final products are, in general, additives. EP of a medium or high sulfur content, which also contain, in general, other hetero atoms. 3) Olefins are reacted with one or more unsaturated bonds, esters, hydrocarbons containing hetero atoms on elemental sulfur or elemental sulfur and hydrogen sulfide, optionally in the presence of a catalyst. The sulfurization of isobutylene or C3 to C8 olefins is most frequently used. Such methods are described in French Patent No. 2,434,864, US Pat. Nos. 3,926,822, 3,899,475, 4,119,550 and 4,119,545, as well as in German Patent No. 2,838,981. these processes, very active EP additives, containing 5 to 50% sulfur. The disadvantage is that it has to operate under a relatively high pressure (100 bar) and at high temperatures (150 to 200 C) and that it appears as secondary products, in a considerable proportion,

polluting substances.

  In the course of research on the subject of the preparation of EP additives, it has now been found that potent EP additives having the general formula (RI-V-Arb) c (Sx) can be prepared much more simply and more economically. Accordingly, the subject of the invention is a process for the preparation of EP additives having the general formula (RI-V-Arb) c (Sx) d in which: RI, RII, RV independently represent each other hydrogen, linear or branched or cyclic, saturated or unsaturated hydrocarbon groups having 1 to 4 carbon atoms, or derivatives thereof, and Ar groups independently of one another are groups of aromatic hydrocarbons with one or more rings (rings) or derivatives of such groups, b represents a number from 1 to 5, c represents a number from 2 to 10, d represents a number from 1 to 9 and x represents a number from 1 to 6. In the process according to the invention, chloromethyl hydrocarbons corresponding to the general formula RI-V-Arb with a solution of formaldehyde and / or paraformaldehyde and hydrochloric acid in aqueous solution and / or gas hydrochloric acid, possibly in the presence of a catalyst, and the reaction is

  Alkylaryl chloride thus obtained on sodium polysulfide.

  As technological research and advanced functional analysis have shown,

  organic solids, for example solubility in lubricating oils and organic solvents, compatibility with other additives,

  are decisively dependent on the composition of the product obtained during chloromethylation. During this stage, it does not appear, in fact, homogeneous substance, but from the beginning of the reaction, it is also formed, next to the monosubstituted compound, disubstituted compounds and optionally polysubstituted. This process is represented in

  reaction schemes A) and B).

  Because of the reaction laws of the alkylaromatic hydrocarbons and, consequently, of the reaction annoyance effect of the -CH 2 -Cl group attached to the aromatic ring, the reaction rate is, when another chloromethyl group intervenes, lower, and the likelihood of intervention of a third chloromethyl group is negligible in

  a large proportion of all cases.

  FIG. 1 shows the composition of the product obtained by chloromethylation of a mixture of isomers of xylene as a function of the total chlorine content of the product (for 35 C and 50 C). The total chlorine content in percent by weight is plotted on the abscissa, the left-hand axis on the left indicates, as a percentage by weight, the content of mono- or di- and polychlorinated product and it has been indicated on the right axis, the relationship between the product

  monochlorine and the dichlorinated product.

  The diagram shows that, when the chlorine content increases, not only the proportion of monochlorine compounds increases (curve I), but that of dichlorinated compounds, that is to say products containing two methyl chloride groups (curve II), also increases considerably. As the chlorine content increases, the ratio of monochlorinated compounds to dichlorinated compounds decreases (curve III). The value of this ratio is lower at

higher temperatures.

  During the first reaction stage of the preparation, it is possible to adjust the corresponding ratio between the monochlorinated and dichlorinated compounds by an appropriate choice of the temperature, the ratio (of the proportion) molar xylene-hydrochloric acid-formaldehyde and the

chlorine content.

  During the polysulfide formation stage, due to Sx bonding, dimers, trimers and possibly tetramers, the product is a mixture. The process is illustrated

  by reaction schemes C), D) and E).

  The reaction according to Reaction Scheme E) proceeds to a perceptible extent only in the case of a high content of dichlorinated compounds. In the preparation of additives, however, the proportion of monochlorinated compounds is a multiple of the proportion of dichlorinated compounds and, therefore, the proportion of tetramers and other oligomers formed during the polysulfide formation stage is negligible. The proportion of extremely complicated compounds forming from compounds

  trichlorinated and polychlorinated, is also negligible.

  FIG. 2 shows the composition of the organic polysulfide as a function of the ratio of the monochlorinated and dichlorinated compounds. The ratio of monochlorinated compounds to dichlorinated compounds is plotted on the abscissa, and the respective content of dimers can be read on the ordinate.

  or trimers, in percentages by weight. The values given for xylene, starting material, were calculated.

  The figure shows that when the ratio of monochlorinated compounds to dichlorinated compounds decreases, the proportion of dimers decreases sharply (I), while the proportion of trimers increases sharply (II). For a ratio of monochlorinated derivatives to dichlorinated derivatives of

  : 1, the product still contains about 12% trimers, while for a ratio of 4: 1 there is already 50% trimers.

  From the point of view of the preparation of EP additives, the ratio of dimers to trimers is of decisive importance in the composition of organic polysulfides. Because their hydrocarbon content is higher, the dimers are better soluble in apolar solvents, lubricating oils, so that as the dimeric content of the polysulfides increases, the solubility of the product increases, and the compatibility with other additives is improving. Polysulfides with a high content of trimers (optionally tetramers) are therefore not suitable for preparing EP additive compositions. This problem arises firstly when thiophosphonates obtained from high molecular weight polyisobutylene are mixed with succinimides; such mixtures are constituents

  important EP additive compositions.

  It has now been found, according to the invention, that in order to prepare organic polysulfides which are also suitable for the preparation of organic additives, an irreducible condition is to adjust the ratio between the monochlorinated and dichlorinated compounds in the chloromethylated product. intermediate to a value of at least 7: 1. Starting from a mixture of isomers of xylene, this condition is fulfilled when chloromethylation is carried out at a temperature of 35 ° C. until a chlorine content of 14% is obtained. Lower chlorine content is uneconomic due to the high proportion of unreacted xylene that remains in this case. At low temperatures, the

  reaction time increases sharply.

  An appropriate composition can also be obtained by performing the chloromethylation at elevated temperatures, but reducing the molar proportion of para formaldehyde. If, for example, chloromethyl is xylene at C until a chlorine content of 12 to 14% is obtained, the molar ratio (the molar proportion) between hydrochloric acid, paraformaldehyde and xylene is 4: 0.6: 1, there is also obtained a product which contains at least seven times more monochlorinated compounds than dichlorinated compounds. The increase in temperature also decreases

  considerably the reaction time.

  As EP additives for lubricating and hydraulic oils, for pasty lubricants (lubricating greases) and liquids for metal machining, as well as for mixing with more strongly polar additives, it is advisable to use organic polysulfides which It is prepared from a chloromethylated intermediate product which contains at least three times more monochlorinated product than dichlorinated product. If a mixture of isomers of xylene is used as the starting material, this condition is fulfilled with certainty if the chloromethylation is carried out at a temperature of at least 50 ° C.

  until a chlorine content of 17.5% is obtained.

  If, in the intermediate chloromethylated product, the content of monochlorinated compounds is not at least three times higher than the content of dichlorinated compounds, the

  solubility of the resulting polysulfide is not satisfactory, the product is not homogeneous and eventually separates into several phases. For a ratio of monochlorinated compounds: dichlorinated as low, oligomers and polymers of higher molar mass are already formed.

  The chloromethylation can be considerably accelerated by the addition of hydrochloric acid gas and, in addition, the proportion of dilute hydrochloric acid which remains after the reaction.

  is lower, but in the product, for the same chlorine content, the proportion of dichlorinated compounds is significantly higher. A similar effect also occurs when Lewis acids are used as catalysts.

  The process according to the invention also extends to the reuse of the diluted hydrochloric acid remaining after the chloromethylation. Its proportion is indeed considerable, because of the quadruple molar excess. Because its HCl content is still relatively high (in

  general, from 24 to 28%), the possibility of reuse exists.

  The recycling of the residual acid is all the more carried out as the HC1 content of the hydrochloric acid appearing

  during the last reaction is less than 15%.

  When the reaction time increases greatly, it can be compensated for by increasing the temperature or using a Lewis acid, as a catalyst, but always taking care to observe the desired ratio of monochlorinated: dichlorinated compounds. The physicochemical properties of the EP 10 additives obtained by the process according to the invention depend strongly on the composition and the structure of the hydrocarbons used as initial compounds. In the first place, the number of carbon atoms and the structure of the alkyl group attached to the aromatic ring are important because they determine the ease of reaction of the alkylaromatic hydrocarbon and have an influence on the properties and properties of the alkyl group. EP effect of

organic product.

  The most important property of the EP additives according to the invention is (besides other important properties, such as the corresponding solubility and other physicochemical characteristics in correlation with the possibilities of use) (viscosity, point of ignition, thermal stability, foam formation), the EP effect that was tested according to the standard prescriptions. These requirements can be found, for example, in

  DIN 51350, ASTM D 2266-67, ASTM D 2783-69T.

  The experiments carried out with the polysulfides have shown that it is necessary to attribute the favorable EP effect, not

  only to the proportion of sulfur introduced into the lubricant, but also to the sulfur-bound organic groups.

  The EP effect of polysulfides containing aromatic hydrocarbon groups is, in general, better, but their solubility is less good. We can improve it

  during chloromethylation, by increasing the ratio of monochlorinated-dichlorinated compounds, as well as by increasing the number of

  and the molar mass of the fixed alkyl substituents

to the aromatic nucleus.

  In carrying out the EP effect tests, it has also been found that the activity depends decisively on the organic polysulfide preparation technology. The purer and more homogeneous product that can be prepared according to the invention is more active than, for example, a product obtained by direct sulfurization of isobutylene, as

  was able to determine it according to the method using a four-ball apparatus and with an FZG tester.

  We will now describe the invention with more

  details of the following non-limiting Examples.

EXAMPLE 1

  In a ground-bottom flask with a heated and cooled ground plug, equipped with a stirrer and a thermometer, 483.5 g of 35% hydrochloric acid and 41.7 g of powdered paraformaldehyde are introduced. The mixture was heated to 50 ° C and stirred until it had completely dissolved (about one hour). The mixture is then cooled to 35 ° C. and 123 g of xylene isomer mixture are added in a molar ratio of 4: 1 HCl-xylene. The mixture is stirred vigorously and chloromethylated until the mixture is stirred. with a chlorine content of 14% (approximately 20 to 25 hours). Thereafter, the stirrer is stopped, the mixture is cooled to room temperature, the chloromethylated xylene constituting the upper phase is separated in a separatory funnel and stripped off.

  traces of hydrochloric acid by insufflation (bubbling) of nitrogen. The composition is determined by gas chromatography.

  Xylene unreacted 38.9% Monochlorine derivatives 57.6% Dichloro derivatives 3.1% Monochlorinated derivatives: dichlorinated 18.6 Chloromethylated xylene freed from hydrochloric acid is reacted with sodium polysulfide of Na2S3 composition. After distilling off the unreacted xylene, the sulfur content of the product is 28.2%. Organic polysulfide has an infinite solubility in xylene, gas oil, pure petroleum ether and lubricating oils. a) The organic polysulfide prepared according to Example 1 is stirred in a ratio of 1: 1 with a mixture comprising an oxidation inhibitor, a dispersant and anticorrosives. The EP additive thus obtained is clear and transparent at room temperature, the opalescence point is 3 ° C. The EP additive is added in a proportion of 6.5% to a SAE-viscosity grade base oil. 8015 W-90. The welding load of the oil with the additive, measured according to DIN 51 350, is 6000 N. During the test of FZG (type: A / 16 6/90/10) of the same oil ,

  performed according to DIN 51 354, the degree of deterioration is greater than 12. Specific mass variation: 0.032 mg / 20 MJ.

  b) The following test is carried out for comparison purposes. As described in Example 1, the xylene isomer mixture was chloromethyl but at 50 ° C until a chlorine content of 17.5% was obtained. Chloromethylated xylene has the following composition (determined by gas chromatography): Xylene unreacted 29.0% Monochlorine derivatives 60.0% Dichloro derivatives 12.0% Monochloro derivative ratio: dichlorinated derivatives 5.0 This xylene is reacted chloromethylated, to produce the organic polysulfide, on a sodium sulfide having the composition Na2S4. An EP additive is prepared as described in Example 1 from the product containing 38.3% sulfur. It is cloudy at room temperature

  and separates into two phases after resting one day.

  Opalescence Point: 38 C. The product has infinite solubility in xylene and gas oil, and partial solubility in pure petroleum ether and oils

  low aromatic content.

  c) The organic polysulfide prepared according to Example 1b) is added to a pasty lubricant (lubricating grease) in a proportion of 3%. This increases its welding load from 2000 N to 5000 N. d) The organic polysulfide obtained according to Example 1b) is added to a cooling and lubricating liquid which can be used for machining the metals in a proportion of 3%. This increases the welding load from 1600N to 5000N.

EXAMPLE 2

  The procedure is as described in Example 1, but the starting material used is not the mixture of isomers of xylene, but pure m-xylene. After 20 hours of chloromethylation until a chlorine content of 14% was obtained, the following composition was determined by gas chromatography: unreacted m-xylene 36.2% Monochlorine derivatives 61.0% 2.7% dichlorinated derivatives Monochlorine derivative ratio: dichlorinated derivatives 22.6 To remove the hydrochloric acid residue, air is bubbled through the chloromethylated xylene. After reaction on a sodium polysulfide of composition Na2S4, the product has a sulfur content of 36.3%. It is soluble in all proportions (infinite solubility) in xylene, gas oil, pure petroleum ether and

lubricating oils.

  The sulfurized product is added in a proportion of 6.5% to a SAE80-W-90 viscosity grade base oil. This increases its welding load, determined with a four-ball machine, to 6500 N (test according to

DIN 51 350).

EXAMPLE 3

  The procedure is as described in Example 1,

  except that the xylene isomeric mixture is chloromethylated at 80 ° C. until a chlorine content of 20% is obtained.

  Composition determined by gas chromatography: unreacted Xylene 22.3% Monochlorinated derivatives 45.9% Dichloro derivatives 27.0% Other 4.8% Monochloro derivative ratio: dichlorinated derivatives 1.7 Chloromethylated xylene is reacted, freed from hydrochloric acid residues by air blowing, on Na2S4 sodium sulfide. The product thus obtained separates, after a short time, into two phases. The upper phase represents 59% of the product, has a sulfur content of 42.1% and is soluble in all proportions in xylene and gas oil, partially in pure petroleum ether and in lubricating oils. The lower phase represents 41% of the product and contains 57% sulfur. It is soluble in benzene and xylene in

  a proportion of 10 g / 100 g of solvent, practically insoluble in pure petroleum ether and lubricating oils.

  The process is not suitable for profitable production

EP additives.

EXAMPLE 4

  The chloromethylation is carried out as described in Example 1, but 220 g of octylbenzene is used as starting material (product) and

  chloromethylation to a chlorine content of 9.1% (about 40 hours). It is determined by chromatography

  gaseous graph, the following composition: unreacted octylbenzene 42.8% monochlorine derivatives 54.5% dichlorinated derivatives 2.7% monochlorinated derivatives: dichlorinated 20.2 To remove the hydrochloric acid residues, the following are bubbled ( Nitrogen is blown into the chloromethylated octylbenzene. The reaction on a polysulfide of composition Na2S4 gives a product with a sulfur content of 24.8%, which is soluble in xylene, gas oil, petroleum ether

pure and lubricating oils.

  6.5% of the sulfurized product is added to a SAE15 80W-90 viscosity grade base oil, the welding load of which, determined with a four-bead apparatus, thus increases to 6000 N (test carried out).

according to DIN 51 350).

EXAMPLE 5

  The procedure is as described in Example 1 except that 285.3 g of the starting material are used.

  dodecylbenzene and the chloromethylation is carried out to a chlorine content of 7.5% (about 70 hours).

  The following composition is determined by gas chromatography: Dodecylbenzene which has not reacted 44.0% Monochlorine derivatives 53.5% Dichloro derivatives 2.5% Monochlorinated derivatives: dichlorinated 21.4 To remove the hydrochloric acid residues, Nitrogen is passed through the chloromethylated dodecylbenzene. After reaction with sodium polysulfide, a product with a sulfur content of 20.6% is obtained. The product, 6.5%, is added to a SAE-80W-90 viscosity grade base oil, which increases its determined weld load by means of a vacuum cleaner.

  four balls at 5500 N (test carried out according to DIN 51 350).

EXAMPLE 6

  The chloromethylation is carried out as described in Example 1, but the hydrochloric acid which remains after the chloromethylation described in Example 1 is used. This hydrochloric acid contains 24% HCl. The chloromethylation is carried out at 50 ° C. until a chlorine content of 14.2% (about 40 hours) is obtained. The following composition was determined by gas chromatography: unreacted Xylene 39.6% Monochlorinated derivatives 55.1% Dichloro derivatives -4.5% Dichlorinated monochlorinated derivatives ratio 12.2 Chloromethylated xylene was removed from the traces

  hydrochloric acid by passing nitrogen therethrough, and then reacted with sodium sulfide Na2S3 composition.

  The product obtained has a sulfur content of 29.6%. The product, in a proportion of 6.5%, is added to a SAE-80W-90 viscosity grade base stock whose weld load, determined with a four-bead apparatus, thus increases.

  at 6000 N (test according to DIN 51 350).

EXAMPLE 7

  The procedure is as described in Example 1, except that 241.8 g of hydrochloric acid is used. This corresponds to an HC1: xylene ratio of 2: 1 (not 4: 1, as before). The chloromethylation is carried out at 40 ° C. until a chlorine content of 14% (approximately 40 hours) is obtained. The following composition was determined by gas chromatography: unreacted Xylene 40.1% monochlorinated derivatives 56.6% dichlorinated derivatives 4.0% Monochlorinated derivatives ratio: - dichlorinated 14.2 Nitrogen was passed through through xylene

  chloromethylated to remove traces of hydrochloric acid.

  The reaction is then carried out on a sodium sulphide of composition Na2S3. The product has a sulfur content of 28.4%. This product was added in a proportion of 6.5% to a SAE-80W-90 viscosity grade base oil, which raised its welding load, measured with a four-bladed apparatus, to 6000 N (test performed according to DIN

51,350).

EXAMPLE 8

  In a round bottom flask equipped according to Example 1, which further comprises a conduit for supplying and evacuating gases, 1800 g of 28% hydrochloric acid and 339 g of paraformaldehyde are introduced. The mixture is heated to 50 ° C and stirred until all of the paraformaldehyde is in solution (about one hour). The mixture is then cooled to 25 ° C. and 1000 g of xylene isomer mixture is added. Hydrochloric gas is then introduced into the mixture. The chloromethylation is continued until a chlorine content of 14.1% (about 18 hours) is obtained. The following composition was determined by gas chromatography: unreacted Xylene 45% Monochlorinated derivatives 45% Dichloro derivatives 10% Monochlorinated derivatives: dichlorinated ratio 4.5 Chloromethylated xylene, freed from hydrochloric acid, was reacted with nitrogen, on a sodium polysulfide of Na2S5 composition. The product obtained has a sulfur content of 41.5% and is soluble in all proportions in benzene, xylene and gas oil. In pure petroleum ether and in lubricating oils, it is soluble

less than 10 g / 100 g of solvent.

  a) The sulphurized product obtained, in a proportion of 3%, is added to a pasty lubricant whose welding load thus increases from 2000 N to 5000 N. b) The product is added, in a proportion of 3%, to a coolant and lubricant useful for machining metals, which

1600 N to 5000 N.

EXAMPLE 9

  For comparative purposes, according to German Patent No. 2,838,981, 526 g of powdered sulfur are introduced into a high pressure reactor equipped with a stirrer, a heating jacket and a regeneration coil. 920 g cooled liquid isobutylene and 269 g liquid hydrogen sulfide also cooled. After closing the reactor, the mixture is heated to 170 ° C. The pressure increases to 92 bar. The reaction mixture is stirred for 10 hours, the pressure slowly decreasing to below 20 bar. The reactor is then cooled to room temperature and its contents, a dark red-brown liquid, are transferred to a distillation flask. After distilling off the unreacted, clarified and purified components,

  760 g of product with a sulfur content of 42.5% are obtained.

  6.5% of the sulfurized product is added to a SAE-80W-90 viscosity grade lubricating oil, which increases the welding load to 3800 N. gear oil containing 6.5% of the additive, the FZG test according to the

  requirements of DIN 51 354 (type: A / 16, 6/9/10).

  The degree of deterioration is 12, the specific mass change is 0.122 mg / MJ.

EXAMPLE 10

  The procedure is as described in Example 1, except that only 21 g of paraformaldehyde is used. The mixture was heated to 80 ° C and stirred for 12 hours after xylene was added. The analysis gives the following results: Chlorine content 13% Xylene unreacted 42.7% Monochlorine derivatives 52.8% Dichloro derivatives 3.5% Monochlorine derivatives ratio: dichlorinated 15.1 Air is passed through through xylene

  chloromethylated to remove hydrochloric acid residues.

  The reaction is then carried out on sodium polysulfide having the Na2S4 composition. The product obtained has a sulfur content of 37.2%, it is soluble in all proportions in xylene, gas oil, pure petroleum ether and

lubricating oils.

  The product, 6.5%, is added to a SAE-80-W-90 viscosity grade base stock, which causes its weld load, determined with a four-ball apparatus, to rise. 6000 N (test carried out according to

DIN 51 350).

Claims (6)

  1) A process for the preparation of an EP (extreme pressure) additive suitable for the preparation of lubricating and hydraulic oils, pasty lubricants (lubricating greases) and lubricating liquids and coolants useful for the machining of metals, corresponding to the general formula: (RI-V-Arb) c (Sx) d in which: RI, RII ... RV independently of one another represent hydrogen, hydrocarbon groups comprising 1 to 40 linear or branched carbon atoms or cyclic, saturated or unsaturated, or derivatives thereof, the Ar groups represent, independently of each other, aromatic hydrocarbon groups having one or more rings (rings), or derivatives of such groups, b is 1 to 5, c is 2 to 10, d is 1 to 9, and 20 x is 1 to 6, reacting chlorinated organic compounds having the general formula : (RI- V-Arb) -Cla in which: a represents a number from 1 to 5, on metal sulfides corresponding to the general formula: MnSx nx in which: M represents an alkali metal and / or alkaline earth metal, n represents the number 1 or 2, and x represents a number from 1 to 6, characterized in that chloromethyl hydrocarbons corresponding to the general formula RI-V-Arb with a solution of formaldehyde and / or paraformaldehyde and hydrochloric acid in aqueous solution and / or hydrochloric gas, optionally in the presence of a catalyst, and in doing so, in order to prepare EP additive mixtures, the ratio of the monochlorinated compounds and the dichlorinated compounds is adjusted to a value of at least 7: 1, to prepare EP additives for lubricating oils and hydraulic oils, pasty lubricants and auxiliaries for metal machining, the ratio of monochlorinated compounds to dichlorinated and poly compounds is adjusted. to a value of at least 3: 1, and the chloromethylated product is then reacted on the   metal sulphide corresponding to the formula MnSx and the final product is optionally purified.   2) Process according to claim 1, characterized in that, to produce sulfur compounds suitable as EP additives for lubricating oils, chloromethyl is a mixture of xylene isomers at a temperature of at most 20 40 C maintaining a molar ratio between hydrochloric acid, paraformaldehyde and xylene of at least 4: 1, 2: 1, until a chlorine content of 12 to 14% is obtained, then the chloromethylated xylene is reacted.   on sodium polysulfide and the product is optionally purified.   3) Process according to claim 1, characterized in that, to prepare EP additives for lubricating and hydraulic oils, for pasty lubricants and for auxiliary products useful for machining metals, chloromethyl is a mixture of isomers of xylene to a temperature of 40-50 ° C., maintaining a molar ratio of hydrochloric acid, paraformaldehyde and xylene of 4: 1.2: 1, until a chlorine content of 14 to 17.5% is obtained, we   chloromethylated xylene is reacted with sodium polysulfide and the product is optionally purified.   4) Process according to any one of claims 1 to 3, characterized in that reutilizes hydrochloric acid, lower concentration, remaining after chloromethylation.   5) Process according to claim 1, characterized in that, to prepare sulfurized compounds suitable for the EP additive mixtures of lubricating oils, chloromethyl is a mixture of xylene isomers at a temperature of at most 100 C in maintaining a HCl-para-formaldehyde-xylene molar ratio of at most 4: 0.8: 1, until a chlorine content of 10 to 14% is obtained, the chloromethylated xylene is reacted with sodium polysulfide, and   the product is optionally purified.   6. Process according to claim 1, characterized in that, to prepare EP additives for lubricating and hydraulic oils, pasty lubricants and auxiliaries useful for machining metals, chloromethyl is a mixture of xylene isomers. at a temperature of 80 to 100 ° C maintaining a molar ratio of HC120 paraformaldehyde-xylene of at most 4: 1: 1, until a chlorine content of 12 to 17.5% is obtained, the xylene is reacted chloromethylated on sodium polysulfide and   the product is optionally purified.